Monomer polymers from

E) POST-FORMED POLYMERS FROM MONOMERS CONTAINING ONE OR MORE DOUBLE BONDS... 

Only one exception to the clean production of two monomer molecules from the pyrolysis of dimer has been noted. When a-hydroxydi-Zvxyljlene (9) is subjected to the Gorham process, no polymer is formed, and the 16-carbon aldehyde (10) is the principal product in its stead, isolated in greater than 90% yield. This transformation indicates that, at least in this case, the cleavage of dimer proceeds in stepwise fashion rather than by a concerted process in which both methylene—methylene bonds are broken at the same time. This is consistent with the predictions of Woodward and Hoffmann from orbital symmetry considerations for such [6 + 6] cycloreversion reactions in the ground state (5). 

When -xylene is used as the monomer feed in a plasma polymer process, PX may play an important role in the formation of the plasma polymer. The plasma polymer from -xylene closely resembles the Gorham process polymer in the infrared, although its spectmm contains evidence for minor amounts of nonlinear, branched, and cross-linked chains as well. Furthermore, its solubiUty and low softening temperature suggest a material of very low molecular weight (15). 

Suitable protective coUoids for the preparation of acryhc suspension polymers include ceUulose derivatives, polyacrylate salts, starch, poly(vinyl alcohol), gelatin, talc, clay, and clay derivatives (95). These materials are added to prevent the monomer droplets from coalescing during polymerisation (110). Thickeners such as glycerol, glycols, polyglycols, and inorganic salts ate also often added to improve the quahty of acryhc suspension polymers (95). 

The Fischer-Tropsch process can be considered as a one-carbon polymerization reaction of a monomer derived from CO. The polymerization affords a distribution of polymer molecular weights that foUows the Anderson-Shulz-Flory model. The distribution is described by a linear relationship between the logarithm of product yield vs carbon number. The objective of much of the development work on the FT synthesis has been to circumvent the theoretical distribution so as to increase the yields of gasoline range hydrocarbons. 

Polyester composition can be determined by hydrolytic depolymerization followed by gas chromatography (28) to analyze for monomers, comonomers, oligomers, and other components including side-reaction products (ie, DEG, vinyl groups, aldehydes), plasticizers, and finishes. Mass spectroscopy and infrared spectroscopy can provide valuable composition information, including end group analysis (47,101,102). X-ray fluorescence is commonly used to determine metals content of polymers, from sources including catalysts, delusterants, or tracer materials added for fiber identification purposes (28,102,103). 

Rayon is unique among the mass produced man-made fibers because it is the only one to use a natural polymer (cellulose) directly. Polyesters, nylons, polyolefins, and acryflcs all come indirectly from vegetation they come from the polymerization of monomers obtained from reserves of fossil fuels, which in turn were formed by the incomplete biodegradation of vegetation that grew millions of years ago. The extraction of these nonrenewable reserves and the resulting return to the atmosphere of the carbon dioxide from which they were made is one of the most important environmental issues of current times. CeUulosic fibers therefore have much to recommend them provided that the processes used to make them have minimal environmental impact. 

The principal chemical markets for acetylene at present are its uses in the preparation of vinyl chloride, vinyl acetate, and 1,4-butanediol. Polymers from these monomers reach the consumer in the form of surface coatings (paints, films, sheets, or textiles), containers, pipe, electrical wire insulation, adhesives, and many other products which total biUions of kg. The acetylene routes to these monomers were once dominant but have been largely displaced by newer processes based on olefinic starting materials. 

Various inorganic, organic, and organometaUic compounds are known to cataly2e this polymerization (4,8,9). Among these, BCl is a very effective catalyst, although proprietary catalysts that signiftcandy lower polymerization temperature from the usual, sealed-tube reaction at 250°C are involved in the industrial manufacture of the polymer. A polycondensation process has also been developed for the synthesis of (4) (10—12). This involves elimination of phosphoryl chloride from a monomer prepared from (NH 2 04 and PCl. ... 

Recycle and Polymer Collection. Due to the incomplete conversion of monomer to polymer, it is necessary to incorporate a system for the recovery and recycling of the unreacted monomer. Both tubular and autoclave reactors have similar recycle systems (Fig. 1). The high pressure separator partitions most of the polymers from the unreacted monomer. The separator overhead stream, composed of monomer and a trace of low molecular weight polymer, enters a series of coolers and separators where both the reaction heat and waxy polymers are removed. Subsequendy, this stream is combined with fresh as well as recycled monomers from the low pressure separator together they supply feed to the secondary compressor. 

Polymerization in Hquid monomer was pioneered by RexaH Dmg and Chemical and Phillips Petroleum (United States). In the RexaH process, Hquid propylene is polymerized in a stirred reactor to form a polymer slurry. This suspension is transferred to a cyclone to separate the polymer from gaseous monomer under atmospheric pressure. The gaseous monomer is then compressed, condensed, and recycled to the polymerizer (123). In the Phillips process, polymerization occurs in loop reactors, increasing the ratio of available heat-transfer surface to reactor volume (124). In both of these processes, high catalyst residues necessitate post-reactor treatment of the polymer. 

Acrylic Polymers. Although considerable information on the plasticization of acryUc resins is scattered throughout journal and patent hterature, the subject is compHcated by the fact that acryUc resins constitute a large family of polymers rather than a single polymeric species. An infinite variation in physical properties may be obtained through copolymerization of two or more acryUc monomers selected from the available esters of acryUc and methacryhc acid (30) (see Acrylic esterpolya rs Methacrylic acid and derivatives). 

The main benefit of the Dow process was control of the polymer architecture. The polymer from the self-condensation process possessed a linear stmcture, but there were other difficulties. The monomer was cosdy and removal of the cuprous bromide by-product was difficult (17) ultimately, scale-up difficulties terrninated the Dow PPS development. However, there was a growing recognition that PPS was an attractive polymer with an excellent combination of properties. 

With as httie as 0.5% hydrolysis of the sulfone monomer, the polymerization stoichiometric balance is sufficientiy upset to prevent high molecular weight polymer from being achieved. The dependence of maximum attainable PSF molecular weight on water content during polymerization can be inferred from Figure 1. 

An excellent review of composite RO and nanofiltration (NE) membranes is available (8). These thin-fHm, composite membranes consist of a thin polymer barrier layer formed on one or more porous support layers, which is almost always a different polymer from the surface layer. The surface layer determines the flux and separation characteristics of the membrane. The porous backing serves only as a support for the barrier layer and so has almost no effect on membrane transport properties. The barrier layer is extremely thin, thus allowing high water fluxes. The most important thin-fHm composite membranes are made by interfacial polymerization, a process in which a highly porous membrane, usually polysulfone, is coated with an aqueous solution of a polymer or monomer and then reacts with a cross-linking agent in a water-kniniscible solvent. 

The addition polymerization of diisocyanates with macroglycols to produce urethane polymers was pioneered in 1937 (1). The rapid formation of high molecular weight urethane polymers from Hquid monomers, which occurs even at ambient temperature, is a unique feature of the polyaddition process, yielding products that range from cross-linked networks to linear fibers and elastomers. The enormous versatility of the polyaddition process allowed the manufacture of a myriad of products for a wide variety of appHcations. 

The use of monomer-polymer doughs has been largely confined to the production of dentures. A plaster of Paris mould is first prepared from a supplied impression of the mouth. Polymer powder containing a suitable polymerisation initiator is then mixed with some monomer to form a dough. A portion of the dough is then placed in the mould, which is closed, clamped and heated in boiling water. After polymerisation, which usually takes less than half an hour, the mould is cooled and opened. This technique could also be usefully employed for other applications where only a few numbers-off are required but does not seem to have been exploited. 

Table 15.5 Vicat softening of methacrylate polymers from monomers of type CHj = C (CHj) COOR CO...

When many moleeules eombine the maeromoleeule is termed a polymer. Polymerization ean be initiated by ionie or free-radieal meehanisms to produee moleeules of very high moleeular weight. Examples are the formation of PVC (polyvinyl ehloride) from vinyl ehloride (the monomer), polyethylene from ethylene, or SBR synthetie rubber from styrene and butadiene. 

Suspension polymerization of water-insoluble monomers (e.g., styrene and divinylbenzene) involves the formation of an oil droplet suspension of the monomer in water with direct conversions of individual monomer droplets into the corresponding polymer beads. Preparation of beaded polymers from water-soluble monomers (e.g., acrylamide) is similar, except that an aqueous solution of monomers is dispersed in oil to form a water-in-oil (w/o) droplet suspension. Subsequent polymerization of the monomer droplets produces the corresponding swollen hydrophilic polyacrylamide beads. These processes are often referred to as inverse suspension polymerization. 

Active polymers from oligoperoxides. Active polymers can be obtained by the free radical polymerization of vinyl monomers with oligoperoxides as the initia-... 

This chapter discusses synthetic polymers based primarily on monomers produced from petroleum chemicals. The first section covers the synthesis of thermoplastics and engineering resins. The second part reviews thermosetting plastics and their uses. The third part discusses the chemistry of synthetic rubbers, including a brief review on thermoplastic elastomers, which are generally not used for tire production but to make other rubber products. The last section addresses synthetic fibers. 

Chapter 12 discusses the use of the various monomers obtained from a petroleum origin for producing commercial polymers. Not only does it cover the chemical reactions involved in the synthesis of these polymers, but it also presents their chemical, physical and mechanical properties. These properties are well related to the applicability of a polymer as a plastic, an elastomer, or as a fiber. 

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